JPH0680091B2 - Method for producing olefin polymerization catalyst - Google Patents

Abstract

An olefin polymerization catalyst prepared by reacting water with a magnesium dihalide in the presence of a phase transfer catalyst and reacting the resulting hydrated magnesium dihalide with reactants including a benzoic acid ester, an alkoxytitanium compound, an organoaluminum halide and a titanium halide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the polymerization of olefins. In other features,
The present invention relates to new catalysts for the polymerization of olefins.

Japanese Patent Application No. 57-30472, filed on February 26, 1982, discloses many new high activity polymerization catalysts. The disclosures of the above patent applications are hereby incorporated by reference. One type of catalyst disclosed is (a) magnesium dihalide,
Reacting a reactant consisting of (b) a benzoate and (c) a titanium compound such as an alkoxytitanium compound to form a first catalyst component and then reacting that component with a second catalyst component consisting of a precipitating agent. And the resulting solid product
It is produced by reacting with a halogenating agent such as TiCl ₄ .

The catalysts of the Examples of the aforementioned patent application were made using commercially available "anhydrous" magnesium chloride.
The term "anhydrous" magnesium chloride is magnesium chloride 1
Conveniently used to indicate magnesium chloride having less than about 1 mole of water per mole. Typically, commercially available "anhydrous" magnesium chloride contains much less than 1 mole of water per mole of magnesium chloride.

In two of our subsequently filed US patent applications, it is possible to improve the activity of such catalysts by ensuring a certain amount of water associated with the magnesium dihalide. Is disclosed.

The addition of water to the hydrocarbon dispersion of magnesium dihalide was subsequently found to be ineffective for producing catalysts for most commercial scale operations due to the tendency to form large solid agglomerates. did. The formation of large solid agglomerates results in inadequate magnesium dihalide reaction in the subsequent steps of catalyst preparation, thus reducing catalyst activity. The presence of large agglomerates will also tend to cause blockages in the pipes where catalysts are generally transported in state-of-the-art commercial scale polymerization processes.

SUMMARY OF THE INVENTION The present invention provides improved catalysts, methods of making the same, and methods of using the same.

According to the present invention, magnesium dihalide and a small amount of water added to a hydrocarbon solvent are mixed in the presence of a phase transfer agent, and the obtained hydrated magnesium dihalide and benzoic acid ester and alkoxytitanium compound are used. And reacting the first catalyst component with an organoaluminum halide to form a solid product, and reacting the solid product with a halogenating agent containing titanium halide to form a catalyst. At that time, the total number of moles of water, including the water originally bound to magnesium dihalide, is 0.5 to 0.5 of the number of moles of magnesium dihalide.
Use it within the range of 1.5 times.

Detailed Description of the Invention The presently preferred magnesium dihalide is "anhydrous" magnesium dichloride. The greatest improvement is observed when the magnesium dichloride starting material contains less than 0.5 mole of water per mole of MgCl ₂ and is essentially free of organic compounds. The water content can be measured by a usual analytical method.
Typically, such methods include Karl Fisher (Kirl
Fischer) titration as well as the use of conventional methods such as X-ray diffraction and elemental analysis to determine the presence of significant amounts of other substances bound to MgCl ₂ , especially MgO.

In the above alkoxytitanium compound, titanium is bound to at least one oxygen atom, and the oxygen atom is at least 1
It is a compound that is bonded to one alkyl group. A preferred alkoxy titanium compound is a compound having the formula Ti (OR) _{4 where} each R is individually selected from an alkyl group having 1 to 20 carbon atoms and each R may be the same or different. is there. The most preferred compounds are those in which each alkyl group has 1 to 10 carbon atoms.

The molar ratio of the alkoxytitanium compound to the metal halide compound can be selected within a relatively wide range. Generally, the molar ratio of alkoxy titanium: magnesium dihalide is about
It is in the range of 10/1 to 1/10, more preferably about 2/1 to 1/2.

The term benzoic acid ester as used generally includes substituted as well as unsubstituted benzoic acid esters. Typical examples include ethylbenzoate, ethyl p-methoxybenzoate, ethyltoluate, ethyl p-butoxybenzoate, and butylbenzoate. Preferred benzoic acid esters are those having 8 to 12 carbon atoms per molecule.

In a particularly preferred embodiment, the benzoic acid ester and phenol are used to make the first catalyst component. The term "phenol" as used herein refers to substituted as well as unsubstituted phenol. Typical examples are phenol, o-methylphenol, m-methylphenol, p-methylphenol, 4-phenylphenol, o-fluorophenol, m-
Fluorophenol, p-fluorophenol, p-sec-butylphenol, p-ethylphenol, p-isopropylphenol, pt-butylphenol, p-methoxyphenol, p-cyanophenol and p-nitrophenol are included.

The presently preferred combination of ester and phenol is the combination of 4-phenylphenol and ethylbenzoate. The total number of moles of 4-phenylphenol and ethylbenzoate used affects the activity and selectivity of the resulting catalyst. Typically, the ratio of the total moles of these two electron donors to the moles of titanium alkoxide is in the range of about 5/1 to 1/5, more preferably 3/1 to 2/1. Most preferably, 1/2 mole of ethyl benzoate is used per mole of titanium alkoxide.

Any known phase transfer catalyst can be used in the present invention. Such a phase transfer agent is a substance that is known to promote the reaction between the reactants existing in different liquid phases having different polarities. Typical examples include quaternary salts and macrocyclic polyether compounds.

Macrocyclic polyesters are described in US Pat. No. 3,987,061, the disclosure of which is hereby incorporated by reference. The term referring to these cyclic polyether compounds is a compound having 15 to 60 atoms in the polyether ring. Preferred is 15-crown-5 and 18-crown-
It is a 6-row crown ether.

The presently preferred phase change agents are the quaternary salt type.
These are disclosed in US Pat. No. 3,992,432, the disclosure of which is hereby incorporated by reference. Preferred quaternary salts have the formula (R ₁ R ₂ R ₃ R ₄ M) ⁺ X ^-1 (wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different monovalent hydrocarbon radicals, From alkyl, alkenyl, aryl, alkaryl, aralkyl and cycloalkyl groups containing 1 to about 25 carbon atoms per molecule with a total number of carbon atoms of about 15 to 25 or more. M is selected from nitrogen, phosphorus, antimony and bismuth, more preferably nitrogen and phosphorus, most preferably nitrogen, X is a halogen atom, preferably chlorine, although in some cases bromine and iodine are also used. it can). Mixtures of quaternary salts can be used if desired. Specific examples of suitable quaternary salts are: ethylhexadecyldimethylammonium chloride, tetra-n-butylammonium chloride (currently preferred), benzyldimethyloctadecylammonium chloride, didodecyldimethylammonium chloride, dodecyltrimethylammonium chloride. Hexadecyltrihexylammonium bromide, Tetraheptylammonium iodide, Tridecylbenzylammonium chloride, Tri-n-butyldecylphosphonium iodide Tetra-n-butylphosphonium chloride Triphenyldecylphosphonium iodide, Trioctyldodecylstibonium chloride , Diheptylmethyldecyl bismuth chloride, etc. are included.

The phase change agent and the added water can be mixed by any suitable method. It is theorized that the water added by the use of the phase transfer agent is well dispersed in the hydrocarbon as relatively small droplets, which contributes to the formation of relatively small particles of hydrated MgCl ₂ . . For best results, the magnesium dihalide should not be mixed with water while the phase transfer agent is present. One method is to premix water with a phase transfer agent, optionally in the presence of additional hydrocarbons, and then mix the mixture with a hydrocarbon slurry of magnesium dihalide. Another less preferred method is to add water and the phase transfer agent separately and simultaneously to the hydrocarbon dispersion of magnesium dihalide. Yet another method is to premix water and a phase transfer agent and add dihalide to this mixture.

The phase transfer agent is used in any amount that can reduce the formation of aggregates in catalyst manufacture. The amount generally relates to the amount of water to be used in this process. Typically, the phase change agent has a molar ratio of added water: phase change agent of about 20/1.
To about 20,000 / 1, more preferably in the range of about 50/1 to about 5,000 / 1. In a more specific example, when tetra-n-butylammonium chloride is used as the phase transfer agent, the mixture of water and the phase transfer agent is
Generally, it will contain from about 0.03 to about 44% by weight phase transfer agent, or more usually from about 0.08 to about 24% by weight phase transfer agent.

The formation of the first catalyst component is carried out by reacting the obtained hydrated magnesium dihalide with a titanium compound and a benzoic acid ester, and optionally and preferably phenol. The reaction is carried out in a suitable hydrocarbon solvent or diluent which is substantially free of water. Examples include n-pentane, n-heptane, methylcyclohexane, toluene, xylene and the like. The amount of solvent or diluent can be chosen within wide limits. The amount of solvent or diluent will usually be in the range of about 20 to about 100 cc / g metal dihalide.

Generally, it is preferred that the hydrated magnesium dihalide and titanium compound be combined within the range of about 0 ° C to about 50 ° C, more preferably about 10 ° C to about 30 ° C. The reaction between the reactants of the first catalyst component is conducted at a temperature within the range of about 15 ° C to about 150 ° C. Typically the reaction is carried out at refluxing the mixture.

It is not absolutely critical that magnesium dihalide and titanium compounds and optionally phenol are at 20 ° C.
Mix within the range of -40C and then mix the mixture between 90-10
The method of heating at 0 ° C. for several minutes, adding the ester at that temperature and maintaining the mixture at a temperature of about 90-100 ° C. to complete the reaction is presently preferred.

The time required to heat the reactants to produce the first catalyst component is generally in the range of about 5 minutes to about 10 hours, but in most cases about 15 minutes to 3 hours is sufficient.

The reaction between the organoaluminum halide and the first catalyst component can be carried out by simply adding the organoaluminum halide to the first catalyst component. However, it is presently preferred to add the hydrocarbon solution of the halide to the first catalyst component.

The temperature used for the reaction of the second catalyst component, ie the organoaluminum halide, with the first catalyst component can be chosen within wide limits. Commonly used temperatures are from about 0 ° C to about 50 ° C.
At or above the range of 20 ° C to about 30 ° C
Temperatures in the range of are most often used. Since heat is generated when the first catalyst component and the second catalyst component are mixed,
The mixing rate is adjusted as needed, with additional cooling to maintain a relatively constant mixing temperature. It should be noted that the order of addition is not important with respect to the mixing of the first and second components, either component may be added to the other component. However, it is preferred to add the second component to the first component. After mixing is complete, stir the resulting slurry for a time sufficient to ensure mixing of the components, generally about 15 minutes to about 5 hours. Then, the stirring is stopped, and the solid product is collected by filtration, decantation or the like. The product is then washed with a suitable material such as a hydrocarbon such as n-pentane, n-heptane, cyclohexane, benzene, xylene to remove any soluble material present. The product is then dried and stored under nitrogen.

The transition metal compound: second catalyst component molar ratio of the first catalyst component can be selected within a relatively wide range. The molar ratio of the transition metal of the first catalyst component to the second catalyst component is generally about 1.
Within the range of 0: 1 to about 1:10, and more typically about 2: 1 to about 1: 3.
And molar ratios within the latter range usually produce catalysts that can be used as particularly active olefin polymerization catalysts.

The reaction between the solid product resulting from the reaction of the first and second components and the halide ion exchange source is generally carried out neat or in a liquid medium in which the halide ion exchange source dissolves. It is generally in a liquid diluent when the product from step (ii) is contacted with a halide ion exchange source. Any suitable diluent can be used. Examples of this include normally liquid hydrocarbons such as n-pentane, n-heptane, cyclohexane, benzene and xylene.

The temperature used in step (iii) can be selected in a relatively wide range and is generally -25 ° C to + 250 ° C, preferably 0 ° C to 200 ° C.
And a temperature of 100 ° C. is most preferred.

The treatment time can be selected within a wide range and is generally within the range of about 10 minutes to about 10 hours. Although the weight ratio of the above-mentioned halide ion exchange source: the product of step (ii) can be selected from a relatively wide range, the weight ratio of the halide ion exchange source: the product of step (ii) is generally about 10: 1. It is in the range of about 1:10, and more usually in the range of about 7: 1 to about 1: 4. Following treatment of the product of step (ii) with a halide ion exchange source, the solid catalyst is washed with a dry (essentially water-free) liquid of said hydrocarbons such as n-hexane or xylene. To remove excess halide ion exchange source. The resulting catalyst is dried and stored under nitrogen.

The presently preferred titanium halide as the halide ion exchange source is TiCl ₄ . In a particularly preferred embodiment TiCl ₄ is used with a halide of silicon such as HSiCl ₃ and / or SiCl ₄ .

The catalyst of the present invention can be used for the polymerization of olefin. Olefins homopolymerized or copolymerized using the catalyst of the present invention include aliphatic mono-1-olefins. The present invention appears to be suitable for use with any aliphatic mono-1-olefin, but is most often utilized with olefins having 2 to 18 carbon atoms. mono-
1-Olefin can be polymerized according to the present invention using either the particle form method, the gas phase method or the solution type method. Aliphatic mono-1-olefins compare to other 1-olefins and / or other ethylenically unsaturated compounds such as 1,3-butadiene, isoprene, 1,3-pentadiene, styrene, α-methylstyrene It can be copolymerized with small amounts of monomers and similar ethylenically unsaturated monomers that do not damage the catalyst.

The catalysts of the present invention can also be used to prepare homopolymers and copolymers of conjugated diolephin. Generally conjugated diolephins contain from 4 to 8 carbon atoms per molecule. Examples of suitable conjugated diolephins include 1,3-butadiene, isoprene, 2-methyl-1,3-butadiene, 1,3-pentadiene and 1,3-octadiene. Suitable comonomers include the above mentioned mono-1-olephins and generally vinyl aromatic compounds in addition to the conjugated diolefins shown above. Some suitable vinyl aromatic compounds are those having from about 8 to about 14 carbon atoms per molecule, including various alkylstyrenes such as styrene and 4-ethylstyrene, and 1-vinylnaphthalene. .

The weight percentage of conjugated diolephin in the copolymerization mixture can be chosen within a relatively wide range. Wt% of conjugated diolephine
Is generally about 10 to about 95% by weight and the other comonomer is about 90 to about 5% by weight. However, the weight percent conjugated diolefin is preferably about 50 to about 90 weight percent and the other comonomers are about 50 to about 10 weight percent.

The catalysts according to the invention are particularly suitable for the production of stereoregular polyprenes and offer many possibilities for high rate as well as low soluble polymer formation.

The polymerization can be carried out in the liquid phase, with or without an inert hydrocarbon diluent, or in the gas phase.
In the case of propylene polymerization, particularly good results have been obtained by working in the presence of an aliphatic or aromatic diluent which is liquid under the polymerization conditions such as propylene, toluene, gasoline and the like.

It is not necessary in all cases to use a cocatalyst with the catalyst of the invention, but it is recommended to use a cocatalyst for best results. Suitable organometallic cocatalysts for use with the present invention may be selected from hydrides and organometallic compounds of metals of Groups IA, II and IIIA of the Periodic Table. Among the organometallic cocatalysts, the organoaluminum compounds described above are preferred as being suitable for use as the second component of the catalyst, the most preferred organoaluminum cocatalysts being, for example, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisopropylaluminum. Decyl aluminum, trieicosyl aluminum, tricyclohexyl aluminum, triphenyl aluminum, 2-
Compounds of formula R ₃ Al that include methylpentyldiethylaluminum and triisoprenylaluminum.
Triethylaluminum is preferred because excellent results have been obtained in the experiments described below.

The molar ratio of the cocatalyst organometallic compound to the transition metal compound of the first catalyst component is not critical and can be selected over a relatively wide range. The molar ratio of cocatalyst organometallic compound to transition metal of the first catalyst component is generally from about 1: 1 to about 1500: 1.
Within the range of. When the cocatalyst comprises at least one organoaluminum compound, typically about 0.25 to 15 mg of titanium-containing component is used per millimole of organoaluminum cocatalyst.

The catalysts are aromatic esters such as triethylaluminum (TEA), ethylanisate (EA), aromatic esters such as ethylbenzoate (EB), methyl-p-toluate (MPT), and diethylaluminum chloride (DEAC). It is preferably used with a multi-component cocatalyst system containing The best selectivity (stereospecificity) is obtained when the TEA: ester molar ratio is about 2: 1. DEAC, when used, serves to increase activity. In a bench test for batch polymerization, the TEA: ester: DEAC molar ratio is generally about 2: 1: 0.5.
~ 3, preferably about 2: 1: 2 is used. For continuous, relatively large scale operation, for example, a TEA: MPT molar ratio of about 3: 1.
It is possible to not use DEAC at all when using TEA and MPT at ~ 5: 1. The amount of chloride remaining in the polymer depends to some extent on the concentration of DEAC, so DEA should be used when the flash process is used to recover the polymer.
It is desirable to reduce the amount of C used.

The polymerization process according to the invention using the catalysts and cocatalysts described above can be carried out batchwise or continuously.
In batch mode, for example, the stirring autoclave is first purged with nitrogen and then with a suitable compound such as isobutane. When using a catalyst and cocatalyst, either of the above may be initially charged into the reactor through the inlet under isobutane purge or they may be charged simultaneously. After closing the inlet, hydrogen, if used, is added and then a diluent such as isobutane is added to the reactor. When the reactor is heated to the desired reaction temperature, for example for the polymerization of ethylene, generally about 50 ° C to about 120 ° C gives the best results. The monomer is then introduced and a partial pressure within the range of about 0.5 MPa to about 5.0 MPa (70-725 psig) is maintained for best results. At the end of the specified reaction time, the polymerization reaction is stopped and unreacted olefin and isobutane are released. The reactor is opened and a polymer such as polyethylene is collected as a free flowing white solid and dried to give the product.

In a continuous process, a suitable amount of solvent or diluent, catalyst, catalyst,
The polymerizable compound, hydrogen when used, is continuously charged in any desired order. The reaction product is continuously withdrawn, the diluent (solvent) and unreacted monomers are suitably, generally flushed, to recover the polymer and the resulting polymer is dried.

In order to obtain optimum productivity of low-solubility polymers in a continuous polypropylene polymerization process, it is preferred to contact the titanium-containing catalyst with a cocatalyst containing a trialkylaluminum electron donor before exposure to liquid propylene.

Olefin polymers made with the catalysts of the present invention are useful in making articles by conventional polyolefin processing techniques such as injection molding, rotomolding, film extrusion and the like.

To further understand the invention and its advantages, the following examples are set forth.

Example 1-Preparation of Polymerization Catalysts MgCl ₂ containing less than about 0.1 mol of water per molecule and sufficient free water mixed with tetra-n-butyl chloride (TBAC) to partially hydrate MgCl _2, ie MgC as a reactant
The production of a typical polymerization catalyst using l ₂ · H ₂ O is described below.

In a 30 gallon (113) Pfaudler reactor
Contains 7.2 gallons (27) of dry mixed xylene (commercially available) and 1.6% by weight of water, previously 30
951.6 g MgCl ₂ sieved with mesh sieve (US sieve system) was loaded. The MgCl ₂ used corresponds to the calculated composition MgCl ₂ .0.09H ₂ O. There is a calculated amount of water. That is, 951.6
× 0.016 = 15.2 g (0.84 mol). The calculated amount of anhydrous MgCl ₂ , 951.6 × 0.984 is 936.4 g (9.84 mol). About 25 ℃
While stirring the mixture at 180 ml (10 mol) water and 8.4 g
A second mixture consisting of (0.030 mol) TBAC was added over 12 minutes. The total amount of water present was calculated to be 10.84 mol.
The calculated free water: TBAC molar ratio added is 333: 1, and the total water: TBAC calculated molar ratio is 357: 1. The resulting mixture was stirred and heated at 40 ° C-50 ° C for 90 minutes. Cool the reactor and contents to about 30 ° C to 35 ° C, and add 1248.7g (7.34mol) of 4-
Phenylphenol (4-pp) and 3.8 lbs (5.06 mol)
Titanium tetra-n-butoxide [Ti (OBu) ₄ ] was added. The mixture was heated to 90 ° C to 100 ° C for 15 minutes, 0.8 lb (2.42 mol) of ethyl benzoate (EB) was added and the stirred mixture was heated at 90 ° C to 100 ° C for an additional 45 minutes.
The reactor and contents were cooled to about 50 ° C. and 10.4 pounds of ethylaluminum sesquichloride (4.78 moles) was added over 60 minutes as a 25 wt% solution in n-heptane. The mixture was stirred for an additional 45 minutes, cooled to about 30 ° C., 5 gallons (19) of n-hexane were added and stirring was stopped. The solid was allowed to settle and the mother liquor was decanted. 15 solids for each wash
Gallon (57) was washed four times with n-hexane, and the washing solution was decanted after each washing. 105.6 lbs (47.9 kg) of TiCl ₄ , 61.2 lbs (27.8 kg) of HSiCl on the washed solids
32.0 lbs (14.5 kg) of a mixture prepared by mixing ₃ and 27.6 lbs (12.5 kg) of SiCl ₄ was added. This mixture contains 54.3 wt% (47.5 mol%) TiCl ₄ , 31.5 wt% (3
8.6 mol% HSiCl ₃ and 14.2 wt% (13.9 mol%)
Was calculated to contain SiCl ₄ .

Heat the mixture to 90 ° C-100 ° C for 1 hour with stirring,
Cool to about 30 ° C., add 5 gallons of n-hexane and stop stirring. The catalyst solid was allowed to settle and the liquid was decanted. The solid was washed 6 times with 15 gallons of n-hexane as above, transferred to a receiver and stored.

About 0.1 per mole of MgCl ₂ is obtained by the general method described above.
It was added to TBAC sufficient free water and variable amounts MgCl ₂ containing the following water mole, the MgCl ₂ of from about 0.9 to 1.25 moles of water are bound form as a reactant, to produce a series of catalyst .

Most of the produced catalysts were analyzed for Ti, Mg, Cl and Al contents.

Amount of free water added per mole of the first MgCl ₂ used,
Table 1 shows the amount of free water per mol of TBAC used and the elemental composition of the catalyst produced.

Comparative catalyst F formed relatively large agglomerates, such as marble sized agglomerates, because it clogged the transport pipe during its manufacture and attempted to remove it from the Hadler reactor to a storage tank.

Example II Polymerization of Propylene A catalyst sample was tested for polymerization of propylene using a liquid-filled 3.8 stirrable stainless steel autoclave for 1 hour at 70 ° C. in the presence of the particular cocatalyst system and hydrogen when used. did. A typical promoter system is, for example, about 7.
54 mmol triethylaluminum (TEA) and 7.5
3.76 mmol methyl p-toluate (MP used in combination with 4 mmol diethylaluminium chloride)
T) and a premix composition containing The resulting TEA: MPT: DEAC molar ratio is about 2: 1: 2.

Before each experiment, fill the reactor with n-hexane dried to about 1/2 of the reactor, then mix the reactor and contents at about 10 ° C or above with stirring at a temperature of 100 ° C or above, such as 135 ° C. Heat for ~ 15 minutes for conditioning. The heating and stirring are stopped, the reactor contents are drained and the reactor flushed with dry nitrogen and then with propylene vapor.

While continuing the propylene purge, the TEA / MPT mixture, solid catalyst, DEAC if used and hydrogen are loaded in that order through the reactor inlet. Close the inlet and add 3 liquid propylene to the reactor. Hydrogen can be added from a pressure vessel of known volume by pressure drop, for example 10 psi. Start heating. When the desired reactor temperature is reached, for example 70 ° C, the reactor is filled with a liquid of propylene and opened to the reactor under an overpressure of about 515 psia (3.55 Mpa) with dry nitrogen. Therefore, keep the liquid full during the experiment.

In each experiment, the propylene feed was stopped, about 5 ml of methanol was forced in with nitrogen, and the reactor was cooled to about 30 ° C. to stop the reaction. The stirring is stopped and liquid propylene is discharged from the reactor into a dry, tared container. Fill the reactor with fresh propylene and stir the contents for a few minutes to wash the polymer. The washed propylene is discharged into a container known as tare.

Collect the polymer in the reactor, dry if necessary, remove volatile hydrocarbons and weigh. The polymer was slurried and stabilized in an acetone solution containing a conventional antioxidant system for propylene, and the mixture was heated in a vacuum oven at 60 ° C for about 3
Heat for hours to remove solvent.

The propylene soluble polymer contained in propylene in a known tare container is measured by heating the container in a vacuum oven at about 60 ° C. until dry. The container is then weighed and the remaining residue is measured. The xylene soluble polymer, the calculated productivity of the solid catalyst, and more specifically other physical properties of the polymer, are measured as disclosed in the above mentioned application number 240,533.

The results obtained are shown in Table II.

All of the above experiments, including comparative experiment 6, used active stereospecific catalysts. Data obtained in inventive runs 1 to 5 and comparatively low in comparative run 6 based on productivity in the range of about 8-15 kg polymer / g solid catalyst / hour and total solubles in the range of about 2.5-3% by weight. Comparison of productivity with relatively high solubles data demonstrates the superiority of the results obtained with the invention catalysts.

[Brief description of drawings]

FIG. 1 is a flow chart showing the steps for producing the catalyst according to the present invention.

Front Page Continuation (72) Inventor Gil Ross Houli, De Yui, OK, Oklahoma, USA. Y & T 1022

Claims (9)

[Claims] 1. A cyclic polyether compound having 15 to 60 atoms in a polyether ring or a compound represented by the formula (R ₁ R ₂ R ₃ R ₄ M) ⁺ X ⁻ (wherein R ₁ , R ₂ , R ₃ and R ₄ is the same or different monovalent hydrocarbon group selected from alkyl, alkenyl, aryl, alkaryl, aralkyl and cycloalkyl groups having 1 to 25 carbon atoms per group, and carbon atoms In the range of 15 to 28, M is selected from N, P, Sb and Bi, and X is a halogen atom) in a different liquid phase with different polarities. In the presence of a phase transfer agent that accelerates the reaction between the reactants present in, the magnesium dihalide and a small amount of added water in a hydrocarbon solvent are mixed, and the obtained hydrated magnesium dihalide and benzoic acid ester and Alkoxy titanium compound and optionally phenol A first catalyst component to form a first catalyst component, and then the first catalyst component and an organoaluminum halide to form a solid product, the solid product and a halogen containing titanium halide. Reacting with an agent, the amount of water added is such that the total number of moles of water, including the water bound to the magnesium dihalide from the beginning, is equal to the number of moles of magnesium dihalide.
A method for producing an olefin polymerization catalyst, which is useful alone or as a component in combination with an organometallic cocatalyst, characterized in that it is used in a range of 0.5 to 1.5 times. 2. A method according to claim 1 wherein the phase transfer agent is used in an amount such that the molar ratio of added water: phase transfer agent is in the range of about 20/1 to about 20,000 / 1. The method described. 3. The method according to claim 1 or 2, wherein M is nitrogen. 4. The magnesium dihalide comprises magnesium dichloride and the alkoxytitanium compound has the formula Ti (OR) ₄ (wherein each R is individually an alkyl group having from 1 to 20 carbon atoms). Selected from the group consisting of the following compounds), wherein said organoaluminum halide comprises ethylaluminum sesquichloride.
The method according to any one of item 3. 5. The method according to any one of claims 1 to 4, wherein phenol is also used in the production of the first catalyst component. 6. The method of claim 5 wherein said ester comprises ethyl benzoate and said phenol comprises 4-phenylphenol. 7. The halogenating agent is titanium tetrachloride, HS
Claims 1 to 6 consisting of iCl ₃ and SiCl ₄ .
The method according to any one of paragraphs. 8. The method according to claim 7, wherein the respective molar ratios of TiCl ₄ , HSiCl ₃ and SiCl ₄ are about 4 / 3.3 / 1. 9. The method according to claim 1, wherein the phase change agent is added to water, and the resulting mixture is added to a hydrocarbon containing MgCl _2. the method of.